Na2[(VO)2(HPO4)2C2O4].2H2O : Crystal Structure Determination from Combined Powder Diffraction and Solid State NMR

The vanadyl oxalatophosphate Na-2[(VO)(2)(HPO4)(2)C2O4]center dot 2H(2)O has been synthesized by hydrothermal treatment. Its structure has been determined and refined by combining X-ray powder diffraction and solid-state NMR techniques. It crystallizes with monoclinic symmetry in space group P2(1), a = 6.3534(1) angstrom, b = 17.1614(3) angstrom, c = 6.5632(1) angstrom, beta = 106.597(1)degrees. The structure is related to that of (NH4)(2)[(VO)(2)(HPO4)(2)C2O4]center dot 5H(2)O, which was previously reported. The vanadium phosphate framework consists of infinite [(VO)(HPO4)] chains of corner-sharing vanadium octahedra and hydrogenophosphate tetrahedra. The oxalate groups ensure the connection between the chains to form a 2D structure. The sodium ions and the water molecules are located between the anionic [(VO)(2)(HPO4)(2)C2O4](2-) layers. The thermal decomposition has been studied in situ by temperature-dependent X-ray diffraction and thermogravimetry. It takes place in three stages, where the first two correspond to water removal and the last to the decomposition of the oxalate group and water elimination, leading to the final product NaVOPO4.